The development of thermal print heads (linear arrays of individually-addressable resistors) has led to the development of a wide variety of thermally-sensitive media. In some of these, known as “thermal transfer” systems, heat is used to move colored material from a donor sheet to a receiver sheet. Alternatively, heat may be used to convert a colorless coating on a single sheet into a colored image, in a process known as “direct thermal” imaging. Direct thermal imaging has the advantage over thermal transfer of the simplicity of a single sheet. On the other hand, unless a fixing step is incorporated, direct thermal systems are still sensitive to heat after thermal printing. If a stable image is needed from an unfixed direct thermal system, the temperature for coloration must be higher than any temperature that the image is likely to encounter during normal use. A problem arises in that the higher the temperature for coloration, the less sensitive the medium will be when printed by heating. High sensitivity is important for maximum speed of printing, for maximizing the longevity of a thermal print head (when used), and for energy conservation in mobile, battery-powered printers. As described in more detail below, maximizing sensitivity while maintaining stability is more easily achieved if the temperature of coloration of a direct thermal medium is substantially independent of the heating time.
One method for printing a direct thermal imaging member uses a thermal print head in contact with a surface of a thermal imaging member. Thermal print heads address one line of the image at a time. For reasonable printing times, each line of the image is heated for about 50 milliseconds or less. Storage of the medium (prior to printing or in the form of the final image) may need to be for years, however. Thus, for high imaging sensitivity, a high degree of coloration is required in a short time of heating, while for good stability a low degree of coloration is required for a long time of heating.
Direct thermal imaging members that are exposed by lasers are known in the art. For example, U.S. Pat. Nos. 5,627,014, 5,153,169, 5,342,816 and 5,534,393 describe and claim imaging media comprising color-forming layers that contain a color-forming composition adapted to undergo a change of color upon increase in the temperature of the color-forming layer above a color-forming temperature for a color-forming time. Direct thermal imaging members described in these patents are exposed by lasers emitting in the near-infra-red (NIR) region of the electromagnetic spectrum (i.e., at wavelengths ranging from about 700 to about 1200 nm) and comprise three separate color-forming layers containing yellow, cyan and magenta thermal color-forming compositions. Each of these color-forming compositions comprises a color-forming compound which can produce the desired color and an infra-red absorber capable of absorbing infra-red radiation and thereby generating heat in the color-forming layer. The three color-forming layers use infra-red absorbers absorbing at differing wavelengths so that each color-forming layer can be imaged independently; for example, specific imaging media disclosed in these patents use infra-red absorbers having peak absorptions at approximately 792, 822 and 869 nm.
Many direct thermal imaging systems comprise a leuco (i.e., colorless) dye that is transformed into a colored compound by heat. Typically, a leuco dye does not absorb sufficient radiation from a laser emitting at a convenient wavelength to provide enough heat to effect the color change. For example, U.S. Pat. Nos. 4,602,263 and 4,826,976 (among many other examples) describe leuco dyes that absorb in the ultraviolet. At present, inexpensive ultraviolet lasers for imaging applications are not readily available. Moreover, it may be difficult to provide transparency to ultraviolet radiation in layers that are not intended to be heated by a laser. Visible wavelengths may be used, but in this case the absorber either needs to be bleached in a region of the final image that is intended to be white (i.e., reflecting as much as possible of incident visible light) or must be incorporated so as to absorb only a small fraction of the incident laser radiation. For these reasons, it is often preferred, as described above, to use lasers emitting in the NIR in conjunction with absorbers that absorb efficiently at these wavelengths but minimally at visible wavelengths. Such absorbers are described, for example, in U.S. Pat. Nos. 5,227,498, 5,227,499, 5,231,190, 5,262,549, 5,354,873, 5,405,976, 5,627,014, 5,656,750, 5,795,981, 5,919,950, 5,977,351 and 6,482,950. Even longer wavelengths in the infra-red, such as the output of gas lasers such as CO2 lasers, may also be used.
It is not necessary that the infra-red absorber be incorporated into the color-forming layer itself, although this may be a preferred option. International Patent Application No. PCT/US87/03249, provides that an infra-red absorber may be provided in a layer adjacent the imaging layer to assist in converting infra-red radiation into heat.
The requirements for infra-red absorbers for use in thermal imaging systems are stringent. Since the sensitivity and the resolution of the image produced are often affected by the thickness of the layers in the heat-sensitive element (since the sensitivity of the system is inversely related to the mass of material required to be heated), it is necessary to provide a high degree of absorption of infra-red radiation within a thin layer, sometimes on the order of 1 micron in thickness. To produce this degree of absorption in a layer containing the other components required in thermal imaging systems, it is necessary that the infra-red absorber used have a high extinction coefficient, of the order of at least about 100,000 Lmol−1 cm−1, and a low molecular weight. In addition, the absorber should manifest its maximum absorption within the range of about 700-1200 nm so that it can conveniently be used with existing near infra-red lasers, and have minimal absorption at visible wavelengths. In the present state of technology, solid state diode lasers emitting at about 760 to 1200 nm provide the highest output per unit cost. YAG and other rare earth doped lasers emitting at about 1000-1200 nm are also useful in thermal imaging processes.
U.S. Pat. No. 5,534,393 provides that where imagewise heating is induced by converting actinic radiation to heat, the imaging medium may receive a non-imagewise general heating prior to or during the imaging step. Such heating may be achieved using a heating platen or heated drum or by employing an additional laser beam source or other appropriate means for heating the medium element while it is being exposed. This patent also provides for the addressing of different layers by controlling the depth of focus of a single laser (emitting at a single wavelength).
U.S. Pat. No. 7,314,704 describes imaging recording media that contain an absorber for laser radiation in conjunction with a colorless leuco dye, an activator and a fixer.
U.S. Patent Application No. 2008-0111877 describes an optical disc bearing a direct thermal imaging composition providing a full-color label that can be exposed by a laser.
Most chemical reactions speed up with increasing temperature. Therefore, the temperature required for coloration in the short heating time available from a thermal print head will normally be higher than the temperature needed to cause coloration during the long storage time. Reversing this order of temperatures would be a very difficult task, but maintaining a substantially time-independent temperature of coloration, such that both long-time and short-time temperatures for coloration are substantially the same, is a desirable goal that is achieved by the present invention.
There are other reasons why a time-independent coloration temperature may be desirable. It may, for example, be required to perform a second thermal step, requiring a relatively long time of heating, after printing. An example of such a step would be thermal lamination of an image. The temperature of coloration of the medium during the time required for thermal lamination must be higher than the lamination temperature (otherwise the medium would become colorized during lamination). It would be preferred that the imaging temperature be higher than the lamination temperature by as small a margin as possible, as would be the case for time-independent temperature of coloration.
Finally, the thermal imaging member may comprise more than one color-forming layer and be designed to be printed with a single thermal print-head, as described in the above-mentioned U.S. Pat. No. 6,801,233. In one embodiment of such a thermal imaging member, the topmost color-forming layer forms color in a relatively short time at a relatively high temperature, while the lower layer or layers form color in a relatively long time(s) at a relatively low temperature(s). An ideal topmost layer for this type of direct thermal imaging system would have time-independent temperature of coloration.
Prior art direct thermal imaging systems have used several different chemical mechanisms to produce a change in color. Some have employed compounds that are intrinsically unstable, and which decompose to form a visible color when heated. Such color changes may involve a unimolecular chemical reaction. This reaction may cause color to be formed from a colorless precursor, or may cause the color of a colored material to change, or may cause a colored material to bleach. The rate of the reaction is accelerated by heat. For example, U.S. Pat. No. 3,488,705 discloses thermally unstable organic acid salts of triarylmethane dyes that are decomposed and bleached upon heating. U.S. Pat. No. 3,745,009 reissued as U.S. Reissue Pat. No. 29,168 and U.S. Pat. No. 3,832,212 disclose heat-sensitive compounds for thermography containing a heterocyclic nitrogen atom substituted with an —OR group, for example, a carbonate group, that decolorize by undergoing homolytic or heterolytic cleavage of the nitrogen-oxygen bond upon heating to produce an RO+ ion or RO′ radical and a dye base or dye radical which may in part fragment further. U.S. Pat. No. 4,380,629 discloses styryl-like compounds that undergo coloration or bleaching, reversibly or irreversibly, via ring-opening and ring-closing in response to activating energies. U.S. Pat. No. 4,720,449 describes an intramolecular acylation reaction that converts a colorless molecule to a colored form. U.S. Pat. No. 4,243,052 describes pyrolysis of a mixed carbonate of a quinophthalone precursor that may be used to form a dye. U.S. Pat. No. 4,602,263 describes a thermally-removable protecting group that may be used to reveal a dye or to change the color of a dye. U.S. Pat. No. 5,350,870 describes an intramolecular acylation reaction that may be used to induce a color change. A further example of a unimolecular color-forming reaction is described in “New Thermo-Response Dyes: Coloration by the Claisen Rearrangement and Intramolecular Acid-Base Reaction Masahiko Inouye, Kikuo Tsuchiya, and Teijiro Kitao, Angew. Chem. Int. Ed. Engl. 31, pp. 204-5 (1992).
In all of the above-mentioned examples, control of the chemical reaction is achieved through the change in rate that occurs with changing temperature. Thermally-induced changes in rates of chemical reactions in the absence of phase changes may often be approximated by the Arrhenius equation, in which the rate constant increases exponentially as the reciprocal of absolute temperature decreases (i.e., as temperature increases). The slope of the straight line relating the logarithm of the rate constant to the reciprocal of the absolute temperature is proportional to the so-called “activation energy”. The prior art compounds described above are coated in an amorphous state prior to imaging, and thus no change in phase is expected or described as occurring between room temperature and the imaging temperature. Thus, as employed in the prior art, these compounds exhibit strongly time-dependent coloration temperatures. Some of these prior art compounds are described as having been isolated in crystalline form. Nevertheless, in no case is there mentioned in this prior art any change in activation energy of the color-forming reaction that may occur when crystals of the compounds are melted.
Other prior art thermal imaging media depend upon melting to trigger image formation. Typically, two or more chemical compounds that react together to produce a color change are coated onto a substrate in such a way that they are segregated from one another, for example, as dispersions of small crystals. Melting, either of the compounds themselves or of an additional fusible vehicle, brings them into contact with one another and causes a visible image to be formed. For example, a colorless dye precursor may form color upon heat-induced contact with a reagent. This reagent may be a Bronsted acid, as described in “Imaging Processes and Materials”, Neblette's Eighth Edition, J. Sturge, V. Walworth, A. Shepp, Eds., Van Nostrand Reinhold, 1989, pp. 274-275, or a Lewis acid, as described for example in U.S. Pat. No. 4,636,819. Suitable dye precursors for use with acidic reagents are described, for example, in U.S. Pat. No. 2,417,897, South African Patent 68-00170, South African Patent 68-00323 and Ger. Offenlegungschrift 2,259,409. Further examples of such dyes may be found in “Synthesis and Properties of Phthalide-type Color Formers”, by Ina Fletcher and Rudolf Zink, in “Chemistry and Applications of Leuco Dyes”, Muthyala Ed., Plenum Press, New York, 1997. The acidic material may for example be a phenol derivative or an aromatic carboxylic acid derivative. Such thermal imaging materials and various combinations thereof are now well known, and various methods of preparing heat-sensitive recording elements employing these materials also are well known and have been described, for example, in U.S. Pat. Nos. 3,539,375, 4,401,717 and 4,415,633.
Prior art systems in which at least two separate components are mixed following a melting transition suffer from the drawback that the temperature required to form an image in a very short time by a thermal print-head may be substantially higher than the temperature required to colorize the medium during longer periods of heating. This difference is caused by the change in the rate of the diffusion needed to mix the molten components together, which may become limiting when heat is applied for very short periods. The temperature may need to be raised well above the melting points of the individual components to overcome this slow rate of diffusion. Diffusion rates may not be limiting during long periods of heating, however, and the temperature at which coloration takes place in these cases may actually be less than the melting point of either individual component, occurring at the eutectic melting point of the mixture of crystalline materials.
Despite the many prior art examples of direct thermal imaging systems, therefore, there are none in which the temperature of image formation is substantially time-independent. In particular, there has not previously been described a method for producing an image in which a crystalline chemical compound is converted to a liquid, or amorphous, form, the liquid form having intrinsically a different color from the crystalline form.